Blown wrinkle varnish base



Patented Feb. 19, 1946 UNITED STATE BLOWN WRINKLE VARNISH BASE William A. Waldie, Oakwood, Ohio, assignor to New Wrinkle, Inc.. Dayton. Ohio, a corporation of Delaware N Drawing. Original application December 22,

1941, Serial No.

424,010, now Patent No. 2.372,212, datedApi-il 10, 1945.

Divided and this application October 26. 1942. Serial No.

9'Clairns.

This invention relates to wrinkle varnish base. and this application is a division of my co-pending application Serial No. 424,010, now Patent No. 2,372,212 dated April 10, 1945, filed December 22, 1941, as a continuation-in-part of application Serial No. 335,615, filed May 16, 1940.-

The primar purpose of this invention is the preparation of a wrinkle varnish base comprising the reaction product of drying oil, oil soluble resin and air at elevated temperature.

Hitherto the preparation of wrinkle varnish base has been considered to require the use of China-wood oil, oiticica oil and other similar drying oils containing conjugated double bonds, or mixtures of them, These oils or mixtures were enerally used either in their raw or natural state or subsequent to preliminary treatment as by blowing, depending on the particular characteristics required in the finished Wrinkle varnish base and the nature of the individual oil or mixture of oils being used.

More recently, as disclosed in copending application Serial No. 312,742, filed January 6, 1940, use has been made of blown dehydrated castor oil as a substitute for the costly drying oils previously used in the preparation of wrinkle varnish base.

I have discovered that a wrinkle varnish base can be produced by chemicall combining unbloWn drying type oil with oil soluble resin and air at elevated temperature. The resulting product exhibits excellent wrinkling tendency with the addition of a small amount of drier in the usual manner. and the resulting composition produces a durable finish particularly characterized by its hardness and toughness.

As typical examples of formulations and procedures according to my invention, but without thereby limiting myself to the specific details of procedure and proportions indicated, thefollowing illustrative examples are given:

Example I Maleic acid resin"; pounds 100-125 Dehydrated castor oil gallons 10- 12 Mineral spirit do r 8 Coal tar solvent do 1- 2 the mixture kept at a temperature ranging between 375 and 400 F. The air blowing is continued for approximately one hour, and the blown mixture is then allowed to cool down to a temperature of approximately 300 F., whereupon the solvents are added. p 1

The maleic acid resin ma be of the type corn mercially available and sold under trade names such as Amberol 801, Beckacite 1110, Beck 1111 and Beckacite 1114, but, of course, alkyd resins made from combinations "of i sin;

glycerine and polybasic acid or anhydride prove suitable.

Example II 7 Amberol 801 pounds Varnish grade linseed oil "gallons" 12 Mineral spirit do 5 Solvesso #2 d0 16 Nuodex cobalt 6% "doc." 14;

In preparing the wrinkle varnish base from the above components, the resin isfirst melted in Four gallons of oil by heating to a temperature of approximately 540 F. The balance of the oil is then added and the mixture heated to approximately 400 F. Air is then blown through the mixture to produce vigorous agitation and the temperature maintained within a range of from 375 to 400 F. until the desired viscosity is obtained. A satisfactory viscosity or end-p may be considered to have been reached who 1 drop falls from a stirring rod with a slight thread-like filament while hot. When this condition has been reached the mixture is withdrawn from the fire and the solvent and drier added thereto.

In this instance, the mineral spirit is that grade of petroleum product of either a paraffinic or naphthenic origin which is commonly known in the trade as turpentine substitute, while Sol vesso #2 is a hydrogenated naphtha having a volatility similar to that of xylol and manufac- Example 111 Amberol F-7 ..pounds 100 Castung Z-3 -gallons. 12

' Mineral spirit do 5 .Toluol do. 24 Nuodex cobalt 6% doperature is held between 375 and'400" F. and air blown through the mixture until the proper viscosity has been attained. The blown mixture is then removed from the fire and the mineral spirit added thereto. The thinned mixture is further diluted by adding the toluol as soon as the temperature has dropped to at least 300 F., at which time the cobalt drier is also added.

It will be noted that Amberol F-7 used in Example III is a rosin modified phenol-formaldehyde type of resin and, therefore, those skilled in the art will understand that other oil soluble and non-reaction phenol-aldehyde resins of the same general characteristics may be used in the practice of my invention. These include resins known by trade names as Beckacite, Durez, Para-dura, Durite, Locto, Paranol, Varcum, etc. In every case an oil soluble and non-reactive quality must be employed.

The fundamental diiference between the method of my invention and the product resulting from the practice thereof and the methods and products of the prior art resides in the fact that wrinkle varnish bases hitherto produced are characterized by the fact that they yield softer films at the same oil lengths than the wrinkle varnish base of my invention. Furthermore, the blown oils commonly usedin the prior art exhibit autooxidizing tendencies due to the fact that they contain intermol cularly dispersed air which results in gradual and continuous oxidation and ultimately leads to separation of part of the oil as an insoluble gel thus rendering the product valueless for use in a varnish and particularly so when the varnish is part of a sprayable composition.

tion will preserve its homogeneous nature and will show no separation for an indefinite period of time. I am unable to offer proof as to the mech- In contradistinction, the product of my invenanism of the reaction which the oil undergoes when treated with air atelevated :temperature in the presence of the synthetic resin asihereinbefore set forth, but it is my opinion that due to the comparatively high temperature used in the blowing operation only thatair which is chemically taken up by the mixture remains in the oil, the temperature of treatment beingsufficient- 1y high to expel any non-combined air, thereby preventing the intermolecular dispersion which appears to be present in the case of blown oils.

According to my invention, oil, as such, is not used in the preparation of the final wrinkle composition for it will be remembered that the oil and synthetic resin are'conjointly serrated. In other words, the oil itself is not subjected to blowing. but rather the combination of oil and synthetic resin, which appears to produce a new product which exhibits novel and valuable characteristics.

though preference should be given to those prod- 'ucts of high volatility such as toluol, xylol, light -1y known as top driers and which tend to form the surface skin which is so desirable in wrinkle compositions. The resinate, linoleate or naphthenate type of drier, characterized by ready solubility, proves very suitable for this purpose.

It will be understood that instead of the de hydrated castor oil and varnish grade linseed oil used in the examples tung oil, perilla oil, oiticica oil, soya bean oil, fish .oil and other like oils having conjugated double bonds or mixtures thereof may be used, the choice depending primarily on the availability and cost. Those skilled in the art will understand that the Castung Z-3 used in Example III is a commercial grade of dehydrated castor oil.

The choice of resin will depend on the desired characteristics of the wrinkle varnish base. As has been noted hereinbefore, rosin modified alkyd resin such as maleic acid resin may be used sati-sfactorily and it will be understood that other polybasic acid or their anhydrides, including phthalic, tartaric, citric and malic may be substituted for the maleic acid or anhydride, although the rosin modified maleic acid resin is preferred from among the alkyd resins. Likewise, other phenol-aldehyde resins may be used in place of the Amberol and Durez resins hitherto mentioned.

Furthermore, natural resins such as Congo. kauri, Batu, Zanzibar, oil soluble Manila, pontianak, etc., may be employed but where such natural resins are used they should first be run to make them oil soluble and the first step of the process hereinbefore described would have to be altered accordingly. In such case. the resin would first be fused, the first portion of the oil added to it, and the temperature raised to a point greater than permissible for proper spraying. A

suitable wrinkle coating composition could be prepared from the product of Example I as follows:

Example IV Parts by volume Wrinkle varnish base 20 Toluol 9 Cobalt drier 1 The cobalt drier may be prepared as follows:

Emmple V Cobalt resinate, linoleate, or naphthenate L pounds 10-15 Toluol orxy101 gallons- 5- 8 Another type of drier suitable for use in Ex- The selection of thinners is a not critical al ample IV may be prepared as follows:

without departing from the approximately one-half or the oil to be incorporated at approximately 580 F., adding the other I 1 part of the oil to the mass and cooling down to Example VI Cobalt linoleate solid pounds China-wood oil fatty acids do Toluol, xylol, petroleum naphtha, etc.

gallons.. 6- 8 It will be understood that metal driers other than cobalt compounds may be used, such as those of manganese. The inherent characteristic 0f the drier to be used is its ability to bring 10 about a rapid formation of a skin on the exposed surface of the film in order to cause the changes in volume between the surface of the film and the interior thereof which lead to the production of a wrinkle surface.

The wrinkle coating compositions of Examples II, III and IV may be further compounded with pigment ground in oil vehicle for the purpose of producing wrinkling enamels, and texture mod ybase of my inventionare adapted to be sprayed and then baked at temperatures of from 200 to 250 F. for approximately one hour to produce a wrinkle finish characterized by its toughness and hardness.

It will be understood that while I have set forth certain specific embodiments of my invention, it

is not my intention to have my inventionlimited to or circumscribed by the specific details of procedure and proportions indicated in view of the 40 fact that my invention is adapted to changes according to individual preference and conditions.

scope thereof as defined in the appended claims.

Iclaim: 1. The method of making a wrinkle, varnish base from naturallresin and unblown drying oil which consists in running natural resin to make] it oil soluble and heat reacting the resin with approximately 400 F. then vigorously blowing air into the mixture for approximately one hour-j while a-temperature of 375 to 400 F; is maintained. 2. The method of making a wrinkle varnish base from Congo resin and unblown drying oil which consists in running Congo resin to make it oil soluble and heat reacting the resin with approximately one-half of the oil to be incorporated at approximately 580 Ff, adding the other part of the oil to the mass and cooling down to approx imately 400 F. then vigorously blowing air into I the mixture for approximately one hour" while a temperature of 375 to 400 F. is maintained 3. The method of making a wrinkle varnish base from Zanzibar resin and unblown drying oil which consists in running Zanzibar resin to make it oil soluble and heat reacting the resin with ap- 7o proximately one-half of the oil to beincorporated at approximately 580 F., adding the other part of the oil to the mass and cooling down to approx imately 400 F. then vigorously blowing air into the mixture for approximately one hour while a temperature of 365 to 400 F, is maintained.

4. The method of making a wrinkle varnish base from Manila resin and unblown drying oil which consists in running Manila resin to'make it oil soluble and heat reacting the resin with approximately one-half of the oil to be incorporated at approximately 580 F., addingthe other part of the oil to the mass and cooling down to approximately 400 F. then vigorously blowing air into the mixture for approximately one hour while a temperature of 375 to 400 F. is maintained. i

5. The method of making a wrinkle varnish base from pontianak resin and unblown drying oil which consists in running pontianak resin to make it oil soluble and heat reacting the resin with approximately one-half of the oilto beiiri- -air into the mixture for approximately one hour while a temperature of 3'75 to 400 F. is maintained.

e. The method of making a wrinkle varnish base from natural resin and linseed oil which consists in running natural resin to make it oil soluble and heat reacting the resin with approximately one-half of the oil to be incorporated at f make it oil soluble and heat reacting the resin with approximately one-half of theoil to be incorporated at approximately 580 F., adding the other part of the oil to the mass and cooling down to approximately 400 F. then vigorously blowing air into the mixture for approximately one hour while a temperature of 3'75 to 400- F. is main-' 1 tained;

8. The method of making a wrinkle varnish base from natural resin and unblown drying'oilv 0 which consists in running natural resin tornake' it oil-soluble and heat reactingthe resin with," approximately one-halfof theoil to be'incorpog rated at approximately 580 it, adding the other part 'of the oil to'the mass and cooling down to approximately 400 F. then' vigorously blowing air into the. mixture for approximately one hour while a" temperature of 375 to 400F. is maintained and subsequently, adding mineral, spirit, and further diluting by adding toluol. v 9. The;method -of making a wrinkle varnish base" from natural resin and unblowndrying oil which consists in runningnatural resin to make it oil solubleandjheat reacting the resin with approximately one-half of the oil to be incorporated at approximately 580 F., addingthe other part of the oil to the mass and cooling down to ap proximately 400 F. then vigorously blowing air into the mixture forapproximately one hour while a temperature of 375 to 400 is maintained and subsequently adding mineral spirit and then adding a cobalt naphthenate drier solution.

' WILLIAM A. WALDIE.

base from natural-resin and dehydrated castor oil which consists in running natural resin to 

